Method and composition for imparting fire-proofness to synthetic shaped articles

ABSTRACT

The invention relates to a composition suitable for rendering a shaped article of a synthetic resin fire-proof, which comprises 1. A. A PRECONDENSATE OF A TETRAKIS HYDROXYMETHYL PHOSPHONIUM COMPOUND AND UREA OR B. A PRECONDENSATE OF A TETRAKIS HYDROXYMETHYL PHOSPHONIUM COMPOUND, UREA AND MELAMINE OR GUANIDINE, 2. A COMPOUND HAVING AT LEAST TWO AMINO GROUPS IN THE MOLECULE AND 3. A METHYLOL RESIN PRECONDENSATE HAVING AT LEAST ONE METHYLOL GROUP IN THE MOLECULE. The invention also includes method of rendering the resin article fireproof with said composition.

ilnited tates Patent [191 Date et al.

[ Dec. 17, 1974 METHOD AND COMPOSITION FOR IMPARTING FIRE-PROOFNESS TOSYNTHETIC SHAPED ARTICLES [75] Inventors: Masakazu Date; ShigekiFukuoka,

both of Takatsuki, Japan [73] Assignee: Toyo Boseki Kabushiki Kaisha,

Kita-ku, Osaka, Japan Filed: Mar. 17, 1972 Appl. No.: 235,861

[30] Foreign Application Priority Data Mar. 22, 1971 Japan 46-16614 Dec21. 1971 Japan 46-104421 [52] US. Cl 260/849, 117/136, 252/81,

260/676 R, 260/68, 260/70 R [51] Int. Cl. D06m 13/28, D06m 13/44 {58]Field of Search....-... 260/849; 252/81; 117/136 [56] References CitedUNITED STATES PATENTS 2,812,311 11/1957 Reeves et al 260/849 3,68l l248/1972 Sello et a1. 117/136 3,644,083 2/1972 Stockel et a1. 252/813,101,278 8/1963 Wagner 252/81 2,927,050 3/1960 Reeves et a1... 260/8492,810,701 10/1957 Reeves et al 260/849 2,772,188 11/1956 Reeves et a1260/849 Primary Examine'r.lohn C. Bleutge Attorney, Agent, orFirm-Wenderoth, Lind & Ponack [57] ABSTRACT The invention also includesmethod of rendering the resin article fireproof with said composition.

1 Claim, No Drawings METHOD AND COMPOSITION FOR TMPARTING FIRE-PROOFNESSTO SYNTHETIC SHAPED ARTICLES This invention relates to a method forimparting fireproofness to a shaped article of a synthetic resin andalso relates to a composition to be used therefor.

It is known to treat a shaped article of a synthetic resin with variousphosphates or halophosphates to render the article flame-resistant orretardant. However, the effect is poor in the durability. In fact whenthe article is subjected to laundering, the agent on the article dropsoff and therefore the flame-retardant effect is quickly reduced.

On the other hand, for products containing cellulosic fibers, it isknown to treat the same with a precondensate of a tetrahis hydroxymethylphosphonium compound (which will be referred to as TH P hereinafter) andmelamine and/or urea or guanidine (British Pat. Nos. 938,989 and882,993). According to this method, a cellulosic textile product isapplied with a solution prepared by adding a hydroxide of an alkalimetal to an aqueous solution of the above mentioned precondensate. Thenthe textile product is dried to a predetermined water content and isthen exposed to an ammonia gas or dipped in an aqueous solution ofammonia. This method is effective to cellulosic textileproducts but isnot so useful for a synthetic resin article because the flame-retardantor resistant effect is lost when the article is laundered.

It is also known to apply a precondensate of THP and melamine and/orurea or guanidine to a cellulosic texprovide a composition and methodfor imparting a durable high fire-proofness to synthetic resin articles.

Another object of the present invention is to provide a method forimparting a durable high fire-proofness to an article comprising asynthetic resin and a cellulosic or proteinic polymer.

Other objects of this invention will be apparent from the followingdescription.

Briefly, this invention provides a composition which comprises l (a)precondensate of a tetrakis hydroxymethyl phosphonium compound and ureaor (b) a precondensate of a tetrakis hydroxymethyl phosphonium compoundand urea and melamine or guanidine, (2) a compound having at least twoamino groups in the molecule and (3) a methylol resin precondensatehaving at least one methylol group in the molecule.

This invention further provides a method for imparting fire-proofness(flame-resistance, flame-retardance and the like) to a shaped article ofa synthetic resin which comprises applying an aqueous solution of theabove mentioned composition to the shaped article, which is thenheat-treated.

One of the important features of this invention is in I least onemethylol group in the molecule, there can be remarkably improved as willbe demonstrated in the Examples to be given hereinlater.

The shaped articles to which the present invention is applicable includeyarns, woven fabrics, knitted fabrics, nonwoven fabrics, papers, filmsand the like made from various polymers such as polyesters, for examplepolyethylene terephthalate, polyethylene terephthalate isophthalate andpolyethylene terephthalate parahydroxyethoxybenzoate; polyamides such aspolye-caprolactam and polyhexamethylene adipamide; acrylic polymers suchas polyacrylonitrile, acrylonitrile-vinyl acetate copolymer andacrylonitrilevinyl chloride copolymer; polyolefins such as polyethyleneand polypropylene; vinyl polymers such as polyvinyl chloride,polyvinylidene chloride, polystyrene and polyacrylate; polycarbonatessuch as polycarbonate obtained from bis-phenol A and phosgene;polyurethanes such as polyurethane derived from polyethylene oxide andpolyisocyanate; polyethers such as polyethylene oxide; and. cellulosederivatives such as cellulose acetate. This invention may also beapplicable to shaped articles made from a mixture of one or more of theabove polymers with cellulose or protein, for example, blended yarns,blended woven or knitted fabrics, mixed woven or knitted fabrics andcomposite films.

The above mentioned condensate (1) may be prepared in a manner known perse. Thus for example, a mixture of the two substances i.e. THP and ureaor a mixture of the three substances i.e. THP, urea and melamine or ofTHP, urea and guanidine is caused to react in an aqueous solution at atemperature of about C. for at least 10 minutes. The particularlypreferable reaction condition is at 100 to 108C. for 30 to 60 minutes.Further, it is preferable that the concentration of THP in the reactionsolution is 30 7O by weight.

The proportions of THP, urea, melamine and guanidine to be used are soselected that the equivalent ratio of the amount of the methylol groupsin THP to the amount of the amino groups in the three others is 1:01 to05, preferably 110.2 to 0.35. In case this equivalent ratio is lznotmore than 0.1, the fastness or durability of the fireproof effectagainst laundering will become low. On the contrary, if said ratio islznot less than 0.5, the reaction mixture will gel to form awater-insoluble product during the reaction.

Examples of THP to be used in the presentinvention are tetrakishydroxymethyl phosphonium chloride (THP C), tetrakis hydroxymethylphosphonium hydroxide (THPOH), tetrakis hydroxymethyl phosphoniumacetate (THPA) and tetrakis hydroxymethyl phosphonium phosphate.

The guanidine to be used for the preparation of the precondensate l maybe in the form of guanidine carbonate, guanidine phosphate or guanidinehydrochloride.

As for the compound (2 having at least two amino groups in the molecule,there may be enumerated urea, thiourea, guanidine carbonate, guanidinephosphate and guanidine hydrochloride. The amount of such compound (2)to be used is preferably 2 to 20 parts per 100 parts by weight of theprecondensate (1). If the amount is higher or lower than the abovementioned, the resulting composition on the shaped article will be lowin the durability or fastness.

For the methylol resin precondensate (3) having at enumeratedprecondensates of methylolmelamine to resin, methylolurea resin,methyloluron resin, methyloltriazone resin, methylolethyleneurea resin,methylolpropyleneurea resin and methylolhydroxyethyleneurea resin. It ispreferable to use 2m 15 parts lulosic or proteinous fibers and then thetextile product is subjected to the treatment of this invention.However, it is preferable to wash the product before conducting thetreatment according to this invenntion.

of such resin precondensate (3) per 100 parts by As flame-retardants forcellulose fibers to be used for weight of the first mentionedprecondensate (1). the above Purpose. there can be enumerated N- Thecomposition comprising theabove explained inmethyl)1dalkylphosphohocarboxyhc e grediems 1), (2) and-(3) is applied to aShaped article condensate of trisazyhdmylphosphme oxide and mein theform of an aqueous solution. It is preferable to thylolmelfdmnle 8precondensate keep the treating solution at a pH of-4 to 8. Therefore,phosphor: njlamlde and methylolmelammej if necessary, an alkalinesubstance which is inert to the In c or lductmg f pretreatment" .texmeprqduct composition such as hydroxide of an alkali metal, for comammg,celluloslc fibers .paddeu m g gi example, sodium hydroxide or potassiumhydroxide is manner with a z g l zfi y added to the treating solutiontoadjust the pH. g i i an ys o is and If desired a latent acid catalystsuch as zinc nitrate, i 3 g i fi y 2 g 2.2 wagshin is magnesium chloridecetyl amine or an organic amine Is He rea e an was 6 l g h stronglyrecommended to remove unreated substances ydrochloride may be added tothe treating solutlon.

. on the synthetic fibers.

The treating solution may be applied to the article by an Suitable meansSuch as S a o t The present invention W111 be explained by referring g ppr ymg r Coa to the following examples.

The content, of the composition (as solid) in the treating solution isgenerally 10 4O preferably 20 EXAMPLE 1 by g A solution consisting of2,560 g. of 98 aqueous so- Preferable e the sohlhoh ls'apphed t0 theartl- 25 lution of tetrakis hydroxymethyl phosphonium chloride that theartleleiretams ahout to y (referred to as THPC hereinafter), 325g. ofurea, 82 Welght 0f e composit on (as solid). g. of melamine and 1,820 g.of water was heated under Then the article is dried and heat-treated.Preferably fl f 0 minutes d h h d prepare a the drying is conducted at70 C. for 3 10 minpC 1 i precondensate (A) utes and the heat-treatmentis conducted at to 30 A l i consisting f 2,250 f an 80 aqueous C for 30Seconds to 5 mmutessolution of THPC, 320 g. of urea and 1,550 g. ofwater y theaheve treatment the Shaped article, P e was heated underreflux for 30 minutes and was then larly textile product is renderedfire-proof(flameres1stquenched to prepare a THpC- precondensate (}3) antor fire-retardant) and the effect of fire-proofness is A li consisting f100 l h l terehigh in r ility r fastness, p i ly against laun- 35phthalate fibers was padded with each of the treating ringsolutions asindicated in Table 1 and was squeezed to The fire-proofing effect isfurther enhanced when the a'wet pick up of 75 to 80%. The Wet fabric wasdried material (Synthetic resin. cellulosic derivative, at 80C. for 8minutes, then heat-treated at C. for from which the shaped article is tobe formed contains 3 i s d w s soaped with a bath of 1 g./liter of aknown fire-retardant such as halogen-containing fire- 40 Soapless Soap(product of Kao Soap Co., Ltd.) at 40 retardant. C. for 5 minutes in adomestic laundering machine. The

Further, when the textile product to be treated acfire-proofness of eachtreated fabric was as shown in cording to this invention containscellulosic or protei- Table l. nous fibers such as cellulose/syntheticfibers mixedor As apparent from Table 1, when treated with asolubendedtextile product, it is preferable that the cellu- 45 tion towhich no urea is added, no sufficient firelosic or proteinous fibers arepretreated or applied with proofness is obtained. The fire-proofness ofan una known fire-retardant which is reactive with such celtreatedfabric is 1.0.

I TABLE 1 Present invention Controls Test No. 1 2 3 4 5 6 7Precondensate A g.) 100 100 100 100 Precondensate B (g.) 100 v 100 100Formu- NaOH (g.) 1.3 1.3 1.3 1.3 1.3 1.3 1.3 lation Urea g.) 5 5 1O 10 00 0 Sumitex Resin (g,) 7 7 0 0 0 0 7 Water g.) 40 40 42 42 52 52 45Before I I Fire-proofness" laundering 6.0 6.0 6.5 6.5 3.0 1.0 2.8(average value After of 4 measure- 5 times 5.5 5.0 5.8 I 5.0 2.0 1.0 1.5ments) laundering TABLE l o ntinued Present invention Controls Test No.1 2 3 4 5 6 7 Results Before laundering 2.5 2.6 3.0 2.9 1.7 1.5

Amount of phosphorus After (7r) times 2.2 2.2 2.6 2.2 1 1 0 0.7

laundering A meth ylol melamine resin precondensate (product of SumitomoChemical Company, Limited. Osaka. Japan). "z By Japanese IndustrialStandard (11S) L-1091-1971- Method D wherein a moisture conditionedsample fabric (width 100 mm., weight 1 g.) was rolled to be of a widthof 100 mm. and inserted into a test piece supporting coil end of thetest piece within the test piece su porting coil until the test and washeld at an inclination of 45 degrees. Then the test piece was heatedwith a flame (whose length was adjusted so as to be 45 mm. in theabsence of the supporting coil) ofa burner adjusted to be in piecestopped burning while melting. Then the burner was adjusted to be in aposition in which a position in which the flame was incontact with thelowermost the flame was in contact with the remaining owermost end ofthe test piece. and the same test was conducted. This operation wasrepeated until the part 90 mm from the lower end of the test piecemelted and burned and the fire-proofness was indicated with the numberof the repetitions.

' By a colorimetric method with molybdic acidv EXAMPLE 2 A twillconsisting of polyethylene terephthalate fibers 20 flux for 60 mmutesand was then quenched to prepare I and cotton fibers (65/35) was treatedin the same manner as in Example 1. The results were as shown in Table2.

of melamine and 910 g. of water was heated under rea precondensate (C).When the same treatment as in Example 2 wasrepeated by using thisprecondensate (C) the same results as in Example 2 were obtained.

Table 2 Present invention Controls Test No. 1 2 3 4 5 6 Precondensate A(g.) 100 100 100 Precondensate B (g) 100 100 100 Formu- NaOH (g) 1.3 1.31.3 1.3 1.3 1.3 lation Urea (g.) 5' 5 0 v 0' Sumitex M-3 (g.) 7 7 0 0 00 Water (g. 1 40 42 42 52 52 Before All All Fire-proofness laundering10.9 11.6 9.8 8.8 burned burned Results Ch gm out out ar en cm.) After 5times .11.6 12.1- 11.1 10.2 do. do. laundering Y of the test piece tothe torn tip was measured to determine the char length.

part remaining unburned of the lower end of the test piece.

piece (70 mm. X 300 mm.) was held with a test piece holder, which wasadjusted so that the lower end of the test piece is at a height of 19mm. above the mouth of a burner (adjusted so that the length of theflame is 38 mm. in the absence of the test piece holder).'Then the flamewas contacted with the middle of the width of the test piece to heat thesame for 12 seconds, and then the flame was removed. Then apredetermined load was fitted to one side of the part remaining unburnedof the lower end of the test piece, the otherside was lifted, and thelength from the lower end of the test piece to the torn tip was measuredto determine the char length.

As will be noted from Table 2, even iftreated with a EXAMPLE 3 Asolution consisting of 1280 g. of an 80 aqueous solution of THPC, 246 g.of guanidine carbonate, 41 g.

EXAMPLE .4

A solution consisting of 128.0 g. of an 80 aqueous solution of THPC, 195g. of guanidine phosphate, 41 g. of melamine and 9.10 g. of water washeated under reflux for 60 minutes and was then quenched to prepare aprecond'ensate (D). By the same treatment as in Example 2 except usingthis precondensate (D), the same results as in' Example 2 were obtained.

EXAMPLE 5 A solution consisting of 2,500 g. of an 80 aqueous solution oftetrahis hydroxymethyl phosphonium hydroxide (referred to as THPOHhereinafter), 325 g. of urea, 82 g. of melamine and 1,850 g. of waterwas heated under reflux for 60 minutes and was then quenched to preparea pre'condensate (E).-A poplin consisting of 100 polyester fibers waspadded with each of the treating solutions indicated in Table 3, andsqueezed to a wet pick up of to Then the wet fabric was dried,heat-treated and soaped in the same manner as in Example 1. The resultsare as shown in Table 3.

Table 3 Test N Present invention Control Formulation 1 2 3Preconclensate (E) (g.) 100 100 100 Urea (g.) 5 O Sumitex M-3 (g.) 7 0 0NaOH g.) 0.5 0.5 0.5 Water 40 40 40 Be ore Results laundering 6.0 6.51.0

Fire-proofness After (Coil method) 5 times 5.8 6.0 1.0 (Average value of4 measurements) laundering '5: By .llS-L-l09l-l97l-Method D.

EXAMPLE 6 the following Composition was squeezed to a wet pick Asolution consisting of 1500 g. of an 80 aqueous solution of THPC, 55 g.of'ethyl triazone, 195 g. of urea and 1100 g. of water was heated underreflux for 60 minutes and was then quenched to prepare a precondensate(F). By the same treatment as in Example 5 by using this precondensate(F), the same results as in Example 5 were obtained.

EXAMPLE 7 A solution consisting of 1500 g. of an 80 aqueous solution ofTHPC, 120 g. of dihydroxyethylene urea, 195 g. of urea and l 100 g. ofwater was heated under reflux for 60 minutes and was then quenched toprepare a precondensate (G). By the same treatment as in 1 Example 5 byusing this precondensate (G), the same results as in Example 5 wereobtained.

EXAMPLE 8 A solution consisting of 1920 g. of an 80 aqueous solution ofTHPC. 244 g. of urea, 100 g. of ethylene bistriazone and 1360 g. ofwater was heated under reflux for 60 minutes and was then quenched toprepare a prccondensate (H). By the same treatment as in Example 5 byusing this precondensate (H), the same results as in Example 5 wereobtained.

EXAMPLE 9 A solution consisting of 2560 g. of an 80 aqueous solution ofTHPC. 250 g. of tri-N-methyl phosphoric tri'amide, 82 g. of melamine and1,820 g. of water was heated under reflux for 60 minutes and was thenquenched to prepare a precondensate (1). By the same treatment as inExample 5 made by using this precondensate (l). the same results as inExample 5 were ob tained.

EXAMPLE 10 4 EXAMPLE 11 A poplin consisting of 100 of polyethyleneterephthalate fibers was padded with a treating solution of up of to Thewet fabric was dried at 80C. for 8 minutes, then heat-treated at 150C.for 3 minutes and was then soaped with a solution of l g./liter ofSoapless Soap at 40C. for 5 minutesin a domestic laundering machine. Thetreated fabric had an excellent flame-resistant property and soft hand.

Composition of the treating solution by weight): Precondensate (A) 65NaOH 0.8 Urea- 3.5 Sumitex M-3 5.3 Cetylamine' 0.5

EXAMPLE 12 A poplin consisting of polyethylene terephthalate fibers wastreated in the same manner as in Example 1 1 except that a treatingsolution shown in the following was used. The treated fabric had anexcellent flame-resistant property and soft hand.

Composition of the treating solution ('70 by weight):

Precondensate (B) 65 NaOH 0.8 Urea 3.5 Sumitcx M-3 5.3 10 dispersion ofstearamide 5.0

EXAMPLE 1 3 A poplin consisting of 100 polyethylene terephthalate fiberswas treated in the same manner as in Example 1 1 except that a treatingsolution shown in the following was used. The treated fabric had anexcellent flame-resistant property.

Composition of the treating solution (7! by weight): Precondensate (A)65 NaOH 0.8 Thiourea 4-.2 Sumitex M-3 5.3

EXAMPLE 14 By the same treatment as in Example 13 except using a 9.3guanidine phosphate instead of 4.2 thiourea EXAMPLE 15 By the sametreatment as in Example 18 except that By the same treatment as inExample 13 except using a solution of 2 g./liter of 30 7c H 0 water and0.2 Sumitex 901 (a methylolethylene urea resin precong./liter of Na COwas used instead of the Soapless densate produced by Sumitomo ChemicalCompany, -Soap solution in Example 18, there was obtained a fab-Limited) instead of Sumitex M-3 in the composition of ric having anexcellent flame-resistance. the treating solution in Example 13, afabric having an excellent flameresistance was obtained. EXAMPLE 20 Bythe same treatment as in Example 18 except that EXAMPLE 16 the followingtreating solution was'used instead of the By the same treatment as inExample 13 except using treating solution containing Pyrovatex inExample 18, Sumitex U-8 (a methylolurone type resin preconden- 15 therewas obtained a fabric having an excellent flamesate produced by SumitomoChemical Company, Limresistance. ited) instead of Sumitex M-3 in thecomposition of the treating solution in Example 13, a treated fabrichaving Composition ofthe treating solution an excellent flamereslstancewas obtained. C by weight): l

- M C 100 4.3 EXAMPLE 1'] 2O (Reactant resin precondensate Rzoduced byMonsanto Co.)

By the same treatment by using 0.7 'KOH instead dam 0d d b of NaOl-l inthe composition of the treating solution in i gig a pr uce y g Example13, a treated fabric having a faborable flame- MCC 300 4.0 resistancewas obtained. igg fig glg by EXAMPLE 18 Wetting agent 0.1

A plain woven fabric consisting of polyethylene terephthalate fibers andcotton fibers (50/50). was padded with the following treating solutioncontaining a com- EXAMPLE 21 mercial flame-retardant for cotton, i.e.Pyrovatex CP d f Cib i AG) was ed to awet By the same treatment as inExample 18 except that pick up of 70 The wet fabric was dried at 80C.for the 9 sol was used instead of the 10 minutes, then heat-treated at170C. for 3 minutes treating Sohmoh 9 h yh f CP h Example d was h soapedi h an aqueous Solution i 1-8, there was obtained a fabric having anexcellent ing 2 g./liter of Na CO at 90C. for 10 minutes.flamereslstahce- Com sition of the treatin solution Pyrovatex CP 40Hamel-roof MC 50 Sumitex 8 (Urea-phosphoric acid precon-(Methylolmelamine resin fl g Produced by Nlppon Senka y precondensateproduced b Sumitomo Chemical Compimy, sumltex 10 Limited) (Urea-fonnahnresin preconden- NH Cl 0 4 sate produced by Surmtomo Chemical Company.Limited) Wetting agent 0.0l Octex E 3 (Softening (agent produced bHodogaya emical Co., Lt (NH4)2HPO-I 5 Then the pretreated fabric waspadded with the following treating solution and squeezed to a wetpick'up v of 7:. The wet fabric was dried at C. for 8 mln- EXAMPLE 22utes, then heat-treated at 160 C. for 3 minutes and was soaped with asolution of l g./liter of Soapless Soap at Procedure of f 18 wasrepeated except 60C. for 10 minutes in a domestic laundering machine. 55h 1h5lead9f the sohplhg f the pl Composition of the treating solution(7c by weight): tlohv the fabnc was dlpped h aqueous of 2 g./l1ter of 30H 0 and 0.2 g./liter of Na CO at'40C. forv 5 minutes, was relaxed with adrum washer at C. for 30 minutes, was then padded with a 2 aqueous 60solution of Polon MF-32 (a silicone softening agent f iag ai fifif 801mmproduced by Shin-etsu Chemical Co., Ltd.), was Precondensate (A) 50squeezed to a wet pick up of 70 and was dried at S Q 3 C. for 5 minutes.The treated fabric had an excel- 523. M3 4 lent flame-resistance andsoft hand.

65 EXAMPLE 23 Even after 20 times of laundering. the treated fabricretained an excellent flame-resistance. For comparison, by treatmentwith only Pyrovatex CP,'n0 noticeable flame-resistance was obtained.

EXAMPLE 19 The procedure of Example 22 was repeated except that afterpadded with Polon MF-32 in Example 22', the

EXAMPLE 24 The procedure of Example 22 was repeated except that aCircular (a relaxer manufactured by K. K. Hisaka Seisakusho) instead ofthe drum washer in Example 22. There was obtained a fabric with anexcellent flameresistance.

EXAMPLE 25 A knitted pile fabric of the following structure made with acircular knitting machine was treated in the same manner as in Example18. There was obtained a knitted fabric with excellent flame-resistance.

Pile l:

Base fabric: Textured nylon yarns (150 d.) Pile: Spun yarns ofpolyester/cotton (30/70 of guages and a weight of 320 g/m. Pile 2:

- Base fabric: Textured nylon yarns (I50 d.)

Pile: Spun yarns of acrylic fiber/cotton (30/70) fiber of 20 guages anda weight of 320 g./m.

EXAMPLE 26 When a plain woven fabric consisting of Cordelan (polychlalfibers produced by Kohjin C0., Ltd.) and polyethylene terephthalate(40/60) was treated in the same manner as in Example 1, there wasobtained a fabric with excellent flame'resistance.

EXAMPLE 27 When a knitted fabric consisting of Kanekalon (modacrylicfibers produced by Kanegafuchi Chemical lndustry Co., Ltd.) andpolyethylene terephthalate (40/60) was teated in the same manner as inExample 1, there was obtained a fabric having excellent flameresistance.

EXAMPLE 28 When a needle-punched fabric (thickness 5 mm., weight 140g./m. made of polyethylene terephthalate staples and cotton fibers(50/50) was'treated in the same manner as in Example 2, there wasobtained a needle-punched fabric high in the flame-resistance.

EXAMPLE 29 A knitted fabric of textured nylon yarns was treated in thesame manner as in Example 2 to obtain a knitted fabric high in theflame-resistance.

EXAMPLE 30 When a curtain cloth consisting of acrylic fibers and rayon(40/60) was treated in the same manner as in Example 18, a highflame-resistance was obtained.

EXAMPLE 31 A plain woven fabric consisting of polyethylene terephthalatefibers and cotton (50/50) was padded with the following treatingsolution containing acommercial resinprocessing agent Permafresh LP (aglyoxal type resin precondensate produced by Japan Reichhold Chemicals,Inc.) and was squeezed to a wet pick up of 65 The wet fabric was driedat 80C. for 8 minutes, then heat-treated at 160C. for 3 minutes and wassoaped with an aqueous solution containing 0.2 g./liter of Na CO at 60C.for 3 minutes.

Composition of the treating solution ("/1 by weight): Permafresh LFCatalyst F 2 (Metallic salt catalyst produced by Ja an Reich oldChemicals, nc.) Pcrmarose T (Polyethyleneglycol type hydrophilicfinishing agent produced by l.C.I.)

Then the pretreated fabric was treated in the same manner as in Example2 to obtain the same results as in Example 2. The crease recovery-0fthis treated fabric was also high.

EXAMPLE 32 A plain woven fabric consisting of polyethylene terephthalateand cotton (50/50) was padded with a 20 aqueous solution of NaOl-L-andsqueezed to a wet pick up of 50%. The wet fabric was then dried to awater content of 10 at 80C. and was treated in epichlorohydrin at 85C.for 4 hours. Then thispretreated fabric was further treated in the samemanner as in Example 2 to obtain the same results as in Example 2. Thewashand-wear property of the treated fabric was also excellent.

EXAMPLE 33 A plain woven fabric consisting of polyethylene terephthalateand cotton (SO/50) was treated in the same manner as in Test No. 1 inExample 2. Then the fabric was padded with the following treatingsolution and squeezed to a wet pick up of 50 The wet fabric was dried atC. for 8 minutes and then heat-treated at C. for 3 minutes.

Composition of the treating solution (7! by weight): Scotchgard FC-208 5(Fluorine type water and oil repellent roduced by Sumitomo 3M Co., td.)lsopropanol l The treated fabric has an excellent flame-resistance andwater and oil-repellency.

EXAMPLE 34 When a blended fabric of polyethylene terephthalate and wool(50/50) was treated in the same manner as in Example 2, an excellentflame-resistance was obtained.

EXAMPLE 35 When an acrylic jersey'was treated in the same manner as inExample 2 and was tested by the U.S. Stan- I dard for the Flammabilityof Childrens Sleep Wear (DOC FEB-71), it was found to have an excellentflame-resistance.

EXAMPLE 36 When a Chinon (promix type fibers of Toyobo, Ltd.) fabric wastreated in the same manner as in Example 2 and was tested the same as inExample 35, it was found to have an excellent flame-resistance.

EXAMPLE 37 Composition of the treating solution (74 by weight):Precondcnsate (A) 50 NaOH 0.6 Urea 2.8 Sumitex M-3 4.0 0.5

Sumitex Accelerator-MX (Magnesium chloride type catalst produced bySumitomo emical Company, Limited) What is claimed is:

l. A composition for imparting fire-proofness to a shaped article of asynthetic resin, which comprises parts by weight of (l) (a) awater-soluble precondensate of a tetrakis hydroxymethyl phosphoniumcompound and urea or (b) a water-soluble precondensate of a tetrakishydroxymethyl phosphonium compound, urea and melamine or guanidine inwhich the ratio of the amount of the methylol groups in the tetrakishydroxymethyl phosphonium compound to the total amount of the aminogroups in the urea, melamine and guanidine is an equivalent ratio of1:0.1 to 0.5, (2) 2 to 20 parts by weight of a compound selected fromthe group consisting of urea, thiourea, guanidine carbonate, guanidinephosphate and guanidine hydrochloride and (3) 2 to 15 parts by weightofa methylol resin precondensate having at least one methylol group inthe molecule selected from the group consisting of methylolmelamineresin, methylolurea resin, methyloluron resin, methyloltriazone resin,methylolethyleneurea'resin, methylolpropyleneurea resin andmethylolhydroxyethyleneurea resin.

1. A COMPOSITION FOR IMPARTING FIRE-PROOFNESS TO A SHAPED ARTICLE OF ASYNTHETIC RESIN, WHICH COMPRISES 100 PARTS BY WEIGHT OF (1) (A) AWATER-SOLUBLE PRECONDENSATE OF A TETRAKIS HYDROXYMETHYL PHOSPHONIUMCOMPOUND AND UREA OR (B) A WATER-SOLUBLE PRECONDENSATE OF A TETRAKISHYDROXYMETHYL PHOSPHONIUM COMPOUND, UREA AND MELAMINE OR GUANIDINE INWHICH THE RATIO OF THE AMOUNT OF THE METHYLOL GROUPS IN THE TETRAKISHYDROXYMETHYL PHOSPHONIUM COMPOUND TO THE TOTAL AMOUNT OF THE AMINOGROUPS IN THE UREA, MELAMINE AND GUANIDINE IS AN EQUIVALENT RATIO OF1:0.1 TO 0.5, (2) 2 TO 20 PARTS BY WEIGHT OF A COMPOUND SELECTED FROMTHE GROUP CONSISTING OF UREA, THIOUREA, GUANIDINE CARBONATE, GUANIDINEPHOSPHATE AND GUANIDINE HYDROCHLORIDE AND (3) 2 TO 15 PARTS BY WEIGHT OFA METHYLOL RESIN PRECONDENSATE HAVING AT LEAST ONE METHYLOL GROUP IN THEMOLECULE SELECTED FROM THE GROUP CONSISTING OF METHYLOLMELAMINE RESIN,METHYLOLUREA RESIN, METHYLOLURON RESIN, METHYLOLTRIAZONE RESIN,METHYLOLETHYLENEUREA RESIN, METHYLOLPROPYLENEUREA RESIN ANDMETHYLOLHYDROXYETHYLENEUREA RESIN.